Prevention of oxidation



Patented Jan. 7, 1936 UNITED STATES PATENT OFFICE .rRnvnNnoN or oxma'non Sidney Musher, New York, N. Y., assignor to Musher Foundation Incorporated, New York, N. Y., a corporation of New York No Drawing. Application January as, 1935,

Serial No. 3,876

1 Claims. (01. 99-11 I This invention relates to the protection'of substances and materials against oxidative' changes,

and more particularly is concerned with the protection of food substances especially in solid form 5 against development of undesired oxidation.

changes.

Deterioration of solid substances, and particur In the shelled nut industryfor instance, there.

is a serious problem due to' the fact that the g0 shelled nuts such as walnuts, pecans, almonds,

etc., turn rancid quite readily. The rancidity of. the nuts is not necessarily related to the rancid-- ity of the oils contained in them. In fact, it is generally well recognized that a nut in its natural 95 form will usually keep much longer without development of rancidity, than will the oil expressed from it-depending entirely upon the length of-time of the exposure of the nutand upon its quality.

30 To meet this' problem which arises in the sale and distribution of shel lednuts, it has been found 1 necessary to pack them in sealed tins or similar to oxidative change, and which products parcontainers, either under vacuum, or in an atmosphere of inert gas ,to remove the possibility of II oxidation. Eve'n'under these conditions it has been found impossible to prevent completely, the setting in of rancidity development, due possibly to the fact that the dissolved or absorbed oxygen may come to the surface and causeor' initiate" In addition, it must be recognized 40 oxidation.

that when shelled nuts are kept .under vacuum ,or inert gas, they may keep fairly well for a period of time, but just as soon as .the container is opened, rancidity sets in almost immediately.

45 In the coffee industry as well, serious difliculties are encountered in inhibiting flavor changes andrancidity of the coffee 011. Coffee undergoes substantial changes as a result of oxidation. When cofiee has been roasted and ground, ran- 60 cidity sets in due to the fact that coffee oil is quite an unstable oil. At the time that rancidity sets in there is a noticeable loss of the fresh coffee flavor. Apbarently there is some change during roasting which increasesathe tendency in the cofss fee towards rancidity and deterioration. Considment of oxidative or a erable' attention has been given to preventing rancidity in coffee oil, and attempts to solve'this problem have been made by grindingfre'sh coffee beans to order, by packing coffee in tin or similar sealed containers under vacuum or inert gases, and by special methods for the distribution of fresh coffee. But even with these developments, the problem has not beenentirely answered. Not only is rancidity a factor in the coffee beans of the better grade, but it is even more impbrtant with the poorer grades of coffee where the flneflavor and aroma are lost so easily. The problem applies=equally to those coifeecompounds in which chicory is.used, and as a matter of fact, is a problem which is presem in a great variety of other dry or substan-. tially dry substances in connection with which oxidation is a serious'factor even though rancidity itself may not be-the factor, and the oxidative changes are manifested in other ways than that of rancidity.

Not only havethe problems notbeen solved" in such industries, but the methods of packaging in specialtypes of. containers and under special 'conditions are elaborate and expensive. 1 Or refer nce may lie-made to milk powders. Whole mil powder has a marked tendency to development of rancidity, while skim milk powder develops a tallowiness or staleness, these changes resulting from either oxidation or. aging.

Accordingly there are a'wide variety of products, both edible or inedible which are subject ticularly when in solid or substantially solid condition, did not lend themselves 110 any readily 5 available method for. preventing oxidative changes, and even special packaging methods did not solve the. problemsof the industries in thls connection, as pointed out above. I

' Among the objects of the present invention is the protection of substances particularly solid'or semi-solid, or substantially solid-against developchanges, both in connection with edible and inedibleproducts.

Other objects include simple and economical"? means. effectively obtaining such results.

Other objects of the present invention include the securing of such results, particularly in connection with edible products wherein the flavor, tasteor other similar characteristics of the foodor edible products may 'or may not be modified as desired.-

Still further objects and advantages of the pres.- ent invention will appear the more detailed description given below, it beingunderstood, how-' ever, that this more detailed description is given.

by way of illustration and explanation only, and not by way of limitation, since various changes therein may be made by those skilled in the art without departing from the scope and spirit of the present invention.

In application, Serial No. 696,915, filed-November 6, 1933, entitled Stable food products, there is described and claimed the protection of glyceride oil bearing materials primarily, including oils and fats and mixtures thereof, against oxidative changes, such as those which result in rancidity, by the use of sesame products. Sesame seed is particularly set forth and claimed therein for that purpose utilizing the sesame seed in any desirable form, such as a flour or pulverized material, or by way of extracts produced from such sesame material and incorporated with the glyceride oil and fat, or similar product. In that disclosure, crushed sesame seed without segregation of oil from the cake may be incorporated with the oil and/or fat to impart thereto remarkably improved keeping qualities, making the resulting product substantially resistant to development of rancidity and markedly changing the flavor and odor and other desirable characteristics of the product. As illustrative of such treatment as given in that application, the crushed sesame seed may be permitted to remain with the oil treated, or after relatively short treatment, such as for 15 minutes at moderate temperatures, for example, approximately 150 C., the sesame seed fibers may be filtered off, or otherwise removed from the treated oil, the latter exhibiting marked keeping qualities, modified fiavor and odor, and yielding at the same time a seed cakeof valuable edible characteristics, not alone for the ordinary purposes for which seed cakes are employed, but also because of the manner of treatment, available for human consumption. The sesame seed in ground condition retaining the oil with the seed fiber may be added to the desired oil and/or fat in the amount of from 5 to 10%, for example, and in most instances not exceeding 20%, although, of course, higher quantities may be utilized if desired. A wide variety of oils and fats are referred to as utilizable in accordance with the treatments set forth in that specification, including the various animal and vegetable oils, both in refined and unrefined condition, and including such products as lard, tallow, oleo stearin, hydrogenated derivatives which may be solid products, etc., paint oils, etc. Such treated oils and fats very markedly increase their resistance to the development of rancidity, and show a marked decrease in the development of fatty acid content on stan'ding, exhibit improved taste and odor, and show a far greater stabilization of color which occurs co-existent with stabilization against development of rancidity, and which is of importance to the paint industry as well as from an 1 fats ormixtures containing the same against development of rancidity, such materials being utilized in a manner analogous to that set forth in connection with the sesame products, and being f the protection of various types of materials other permitted to remain in the products themselves, or when desired, removed therefrom. The methods of treatment may be by direct infusion as set forth above, or by utilizing solvent extracted components, either by means of volatile 5 solvents or the glyceride oil extracts themselves, from such seed and oil products. vAmong the nut, seed and fruit products which may be utilized in protecting such glyceride materials against development'of rancidity, or other aging changes, there is particularly set forth the use of peanuts, sunflower seed, cottonseed, linseed, cocoanut, etc. utilized in the protection of a wide variety of oils and fats, such as those illustrated above.

In specification, Serial No. 710,727, filed February 10, 1934, entitled Products from fats and oils and methods of making same, there is particularly described and claimed the protection of glyceride containing materials, such as fats and oils, or mixtures thereof, against oxidative 20 changes, such as development of rancidity, by the utilization of non-oil bearing vegetative matter, such non-oil bearing vegetative matter being materials which either contain no oil whatsoever, or only such minorquantities of oil that they do not 25 serve as a source of oil for commercial or. industrial use. The materials illustrated therein as non-oil bearing substances that may be employed include oats, rye, barley, hominy, alfalfa, and flours, suchas bleached flour and other forms 30 of cereals, as well as ordinary leaves, or even such products as twigs. These non-oil bearing vegetative matters are employed in the manner set forth above for the sesame products, and may be utilized by direct infusion or the glyceride fat or oil con- 35 taining materials to protect them against development of rancidity, either with or without removal of the fibers of the products subsequently, or solvent extracted portions of such non-oil bearing vegetative materials may be utilized for protection of the glyceride materials against development of rancidity.. i

In specification, Serial No. 733,517, filed July 2, 1934,. entitled Foodstuffs, there is particularly described and claimed the utilization of soya bean products in' protecting the glyceride materials against development of oxidative changes such as rancidity, the soya bean material being utilizable -in any desired form, either in the form of the tracted components of the soya bean material incorporated with the glyceridelmaterial to be protected against development of rancidity.

It will be noted that in the prior specifications 'as described above, the. oil containing and non-oil containing vegetative matters are utilized pri- I marily for the protection'of glyceride containing materialssuch as oils and fats or mixtures 65 thereof, or compositions containing them, against oxidative ,or aging changes, particularly as exemplified in the development of r a'ncidity.

In specification, Serial No. 799; filed January 7, 1935, entitled Antioxidants, there is particularly described and claimed the utilization of these vegetative materials, as'set forth above, including both the oil containing and non-oil containing substances, and extracts derived from them, in

than the oil or fat containing substances against oxidative or aging changes. As illustrative of the antioxidant protectants, various oil bearing nuts, seeds and fruits are referred to, including, for example, sesame seed, peanuts, su'nflower seed, cottonseed, poppy seed, linseed, cocoanuts, soya bean, castor bean, etc., whereas illustrating the non-oil hearing or substantially non-oil bearing vegetative matters that may be utilized are the variouscereals and grains, etc., including oats, wheat, rye, barley, hominy, corn, alfalfa, and their various products such as the flours, bleached or unbleached, and other forms of the grains and cereals, as well as such vegetative materials as ordinary leaves, such as maple tree leaves, and

even twigs. Various forms of these products, as

noted, may be employed. Illustrating such types of products, for example, we may utilize the dry,- ground soya bean material, or the soya bean cake from which the oil has been expelled, or the highly refined bleached soya bean flour, or the soya bean material in almostany type of form. As set forth in that specification, these various products may be utilized in treating and protecting various types of substances, including milk powders, including chocolate or other flavored milk products, etc., cheeses, fruit juices, essproducts including egg whites and egg yolks, cod livers and oils, coffee and coffee products, yeast, cocoanut juice and similar juices, rubber and rubber compositions, mineral oils and mineral oil distillates including gasoline, lubricating oils, min-i form of discrete masses, against development of oxidative or aging changes. Particularly impor-- tantin this connection is the utilization of the various vegetative materials set forth above, including both the oil-containing seeds, nuts and. fruits, or derivatives of them, and the substantially non-oil containing vegetative materials, such as the cereals, grains, etc.

It has been found unnecessary to apply the antioxidant materials, or the derivatives containing the antioxidant fa'ctors, in liquid condition, or to products which are to be protected against rancidity which exist in liquid form, or are convertible into liquid form, although of course, the utilization of the liquid state is .a convenient means for producing intimate contact between the source of antioxidant activity and the product to be protected. The importance of this is recognized by the fact that no satisfactory means of preventing oxidative or aging changes in substantially solid products have been available'in the art, which emphasizes why theprior art utilized special packaging means as illustrated above in connection with solid products, such as shelled nuts, coffee, etc. Furthermore, in many cases, such as those just mentioned, it is'impossible or sometimes'inadvisableto utilize a liquid medium as the means for obtaining the intimate operating in a substantially'dry state, or where possible utilizing a. liquid medium, and subsequently converting the product into a substantial 1y dry condition. A number of examples illustrative of the present invention are set forth below.

' sired, those given I ,the means that may be employed in the treating tion ofthe antioxidant extracted material with be available for use For example, in the case of shelled nuts, which I oxidize or turn rancid very rapidly when exposed oil bearing materials utilized as a'source of the to the air, it is found satisfactory to apply a thin film of the antioxidant material, such as oat flour, on the outside of the nuts. This may be is done by any desirable means, such as'by spraying or blowing a finely milled oat product, for exampie, on the shelled nuts, merely leaving as much of the oat flour on the nuts as is required to cover substantiallythe exposed portion. Another 16 method would be merely to dip the nut into the oat flour, and then to .blow away by means of a cin'rent of air, or other gas, most of the oat flour. In this manner that portion of thesurface which has been cut, or the surface upon 15 which there is any nut oil which has been brought out during the shelling operation tends to hold the oat flour inposition. More substantial adof the shelled nuts'by at least double, as compared with-uritreated nuts. On the other hand, underconditions where the presence of the oat flourin a more substantial amount does not so prove undesirable, there may be left on the surfaces from 2 to 5% of oat flour in contact with the surface of the nut or other materials.

Crushed nuts may be treated in the same way,

but desirably the nuts may be crushed in the SI presence of the antioxidant material, such as the cat flour, so as to obtain a fine dispersion of the oat flour through the nuts at the time of grinding or crushing. It should also be borne in mind that the character of antioxidant material employed will determine whether. or not there is any substantial change in taste or odor of the shelled product. Materials like oat flour, and in general the grains and cereal flours not having any great or appreciable change in the taste or odor of the treated products, whereas other materials like sesame derivatives may be. utilized to materially affect and modify the flavor, taste and odor of such products.

The particular 'manner of incorporating the antioxidant material with the solid products or substantially solid materials, particularly when in the form of discrete masses, may vary as deabove illustrating some of of shelled nuts or other products as set forth be-'- low. Other means include, of course, the utiiization of extracts, particularly in volatile solvents, from which extracts the .volatile solvents may be readily eliminated, eitherbefore the incorporathe product to be protected, or after the volatile solvent extract has been applied, and substantially immediately removed from the product treated. Of course, some of the methods will with some products, while others will be required in connection with products of different types, depending on the nature of the materials to be protected against antioxidant activity, and their condition and utility, as well as the nature of the antioxidant material being employed.

Again it should be noted while oat flour is particularly utilized as illustrative in connection with the utilization of antioxidant materials, any of the vegetative materials referred to above may be utilized, and we may particularlymention in addition to the oat flour, such products as barley, hominy, soya bean flour, crushed sesame seed, crushed peanuts, crushed linseed cake, soya bean press cake, castor bean pumace, corn germ cake, corn gluten, etc., either in and of themselves in any of the desirable forms, such as flours, press cakes, etc., or extracts thereof, etc.

In addition to the shelled nut field, a somewhat related development is in connection with the protection of various seeds or beans that ordinarily tend to deteriorate rapidly, either as a result of oxidative or aging changes, and any of which seeds and beans or similar products may be protected in a manner analogous to that discussed above in connection with the shelled or crushed nuts.

Coflee, as has been pointed out, undergoes substantial changes as a result of oxidation or aging. Coiiee products, including coffee beans, may accordingly be treated in accordance with the present invention to protect them against such oxidative or aging changes. The coffee beans may be treated, for example, with the cat flour at the time that the beans are shipped from the place of production, but since most of the deterioration in the coffee beans takes place after the beans have been roasted, it is more desirable to treat the coffee beans with the cat flour foiiowing the roasting operation. While it is true that some of the antioxidant materials, such as the oat flour referred to illustratively, will be left after grinding, so that the product may no longer be termed a pure .coffee material, the presence of the oat flour will in no way prove undesirable from the standpoint of taste or flavor. Consequently, in the manufacture of coffee compounds, where modification of flavor by the added antioxidant material would be undesired, such relatively bland materials as oat flour can be used to a substantial degree, avoiding any flavor change which under such circumstances is negligible. The invention is particularly applicable to the protection of the cheaper grades of coffee and cofiee compounds against oxidative changes, because the delicate aroma of these products is lost so very easily.

By the utilization of these means of protecting cofifec and coifee compounds, the necessity for use of tin or other sealed containers, or of storing under inert atmospheres or vacuum, is substantially eliminated by the utilization of any of these antioxidant materials applied as desired, for example, particularly emphasizing such materials as the cereal flours, including oat flour, or crushed sesame seed, where change in flavor, etc. is not undesirable, etc.

Instead of using the cereal flours as set forth above in the protection of coffee and cofiee compounds, finely ground unroasted coffee beans may themselves be utilized as an anti-oxidant to protect roasted coffee from deterioration, using for example 2% of the finely ground unroasted coffee beans. In this way, the tendencytowards' rancidity and deterioration which is developed in the coffee bean by roasting, may be protected against by the utilization of the unroasted coffee beans, for example, employing about 2% of such material in connection with the coffee beans, and thus avoiding the introduction 01' non-coffee type substances like oat flour if it is considered inadvisable to utilize oat flour or similar materials.-

Further, itmay be noted that although there are such products as corn flakes, wheat flakes,

etc. on the market, there is no such product as oat flakes available, because of the fact that when the oat product is roasted, it apparently itself turns rancid quickly. 'Ihis effect is apparently quite strange in view of the presence in the 5 oat flour itself of antioxidants, and also in view of the fact that the cat flour contains as little as 4% of oat oil. But apparently the roasting process in some way makes the oat product susceptible to relatively rapid development of rancidity. The roasted oats or roasted oat flour may, however, be made available for utilization in the art in accordance with the present invention by treating such roasted oat product with unroasted oat flour, for example, utilizing 5% of fresh oat flour, or by any of the other flours, etc. referred to above. A mechanical mixture of the two is sufficient to pass on to the roasted oat flour the necessary antioxidants. However, if desired in order to get more intimate combination than is available by 20 mechanical mixture, the admixture of fresh oat flour with the roasted oat flour may be dissolved in water, or admixed with water, and immediately thereafter spray dried in order to produce a re-. sulting product that is substantially dry, and 25 which consists of a thorough admixture of the two oat flours. The fresh oat flour is considered the more desirable product to utilize in connection with producing oat products of this character, rather than the other cereal or grain flours, 30 etc, but of course the latter may be utilized if desired.

Similarly the cereals and grains, etc., as exemplified by oat flour may be used in conjunction with spices, either ground or whole, in order to inhibit undesired oxidative changes in such spices which result in deterioration or loss of fiavor'of the product, even though rancidity itself may not be adirect factor in this case.

Cheeses may be rubbed with any of these antioxidative substances, including, for-example, the cereal flours, and particularly oat flour, to inhibit oxldative changes therein or aging effects due to oxidation or other causes, which may desirably be inhibited by this manner of treatment. M

The various powdered milk and cream products may similarly be protected against undesirable oxidation or aging changes by the present invention. Mere mechanical mixture, for example, of an oat flour with the whole milk flour may be em- 50 ployed, or similarly oat flour may be mixed with skim milk powder to inhibit the development of tallowiness-or staleness.

In connection, however, with such products as these dried milk products, instead of mere mechanical admixture, such as for example, the incorporation of 10% of oat flour in the milk powder, either whole or skim milk powder, it is possible to produce the final dry product by adding the desired antioxidative substance, such as the cat flour. to the milk, either whole or skim, before the drying operation, or extracts of the antioxidative substances may similarly be employed. Thus, for example, oat flour may be homogenized with liquid milk, and the resulting product subsequently spray dried, resulting in a substantially dry composition in which the parti:- cles of the dry milk are intimately incorporated with the anti-rancidity protectant.

Similarly at the time of manufacture of the milk powder, a small quantity of finely ground, unroasted cocoa beans may be added to the liquid milk, and the mixture subsequently spray dried in order to insure the protection of that milk against oxidative change. "Ijhe ground cocoa beans may. 7

obtain the more intimate combination of the sub-- I stances by the utilization of the liquid milk for incorporationwith the antioxidative ingredient, followed by the spray drying operation.

Such methods as those which can be employed with the milk prior to the spray drying operation illustrate means of utiliz ng the present'invention in the protection of substantially dry products protected by the vegetative materials, for example, against deterioration due to oxidative or aging changes, wherein the liquid state is employed in one stage of operations.

These various vegetative materials may also be employed in the protection of milk chocolate or similar products for which purpose'2%, for example, of finely ground unroasted cocoa beans may be added -to milk chocolate or similar products. in any of its stages of manufacture, and such addition will substantially inhibit deterioration of the whole milk or similar products that may be used in that milkproduct. Even though coco button of itself exhibits a fairly satisfactory keeping quality, of itself it is not sufiicient to pro- .tect the fat of the whole milk from deterioration,

andthe incorporation of the unroasted cocoa bean in the manner set forth above gives that added protection which materially increases the reten tion of desirable characteristics in the products.

As further exemplifying the utilization of a liquid stage through which the product maybe passed in the production of substantially dry products protected against oxidative orfaging changes, mention may-also be made of the iiicorporation of these vegetative materials, or extracts of them, with liquefied or melted fats or oils that are normally solid .at ordinary temperatures. Such oils and fats when-liquefied or melt- 'ed may thus be directly infused with the vege-' tative material, and the resulting product permitted then to cool to substantially solid condition, while retaining the incorporated vegetative material to protect such products against development of rancidity or other oxidative changes. Or if desired, in such cases, the liquefied or melted oil or fat after direct infusion or incorporation of the vegetative material may have thefibers of n the latter removed before the product is permitted to solidify-by the utilization of any means, suchas filtration, etc.

Or the liquefied condition can be utilized in connection with such products as oils and fats which lend'themselves', at least in some instances v to solution in various organic solvents, particularly of-volat'ile character,- such'solutions being utilized for-contacting with the vegetative materials, or extracts of them-followed by elimination of the solvents whereby the substantially solid. material is obtained carrying the. antioxidative ingredient.

As briefly mentioned above, solvent extracts of the vegetative materials carrying the antioxidant tact .of the cereals or crushed seeds with ethyl material, such as see from .02 to l%.

its life from seven to ten-fold. Where the ex-' other cases, the volatile solvent is first removed 'and food ingredients has been particularly set ,or, ordinary alcohol. Where anoil containing or nuts, is being extracted, a solvent is more desirably chosen which does not substantially remove the glyoerides. from the material, so that the extract is substantially free 5 from oil or fat. Where the material is substantially oil free any solvent may be utilized. The extract may be filtered to remove residual vegetative fibers, or where presence of the fibers is not undesirable, filtering is not necessary.

fective in its antioxidant activity, whereas in other cases, as oat flour extract in alcohol, the difference is not so marked. In general, the alcoholic type of extraction'media remove considerably less of the oils present than do the gasoline types of. extraction media. An alcohol extract of whole pulverized oatsis substantially free of oat oil, while a gasoline extract may con- I tain the entirei to 5%. of oat ofl present in the 20 cats. The alcoholic extract of soya bean oil is also substantially free'of oil. The gasoline type of extraction may, if desired, be applied to the press case left after'oil expression or expulsion, as for example in the case of the soya bean press cake. :5

But here too avoidance of the presence oi oil may be desirable by utilizing the alcoholic type of extract. The extracts may be utilized as such,

or more desirably the volatile solvent may be distilled out, and the residue employed as a con- 30 centrate of antioxidant activity. In, generaL- such'residues obtained, for example, byvacuum distillation and removal of the alcohol leaves -.a

resultant concentrate of somewhat dark color andagreeabl'e odor, but usually neither the color nor 35 odor materially affects the products with which the concentrate is used, particularly since as a general rule the percentages of such concentrates employed may be very small, as for example As illustrative of such extracts, an ethyl alcohol extract of oat flour can bemade by the batch process obtaining 3% of the oat .flour during the alcoholicextraction. '.1%' of such concentrate added to vcastor oil-increases 45 tracts tend to deposit crystals following mixture with a concentrate,- such as a liquefied oil 'or'fat, such crystals may if desired lie removed by filtration;

Any of these various extracts may be utilized in accordance with the present invention. The extract in the. volatile solvent-may be utilized forapplication to the product tobe protected against development of rancidity, and the sol-, vent media subsequently evaporated away. In

from the extracted antioxidant material, and the latter in substantially solid or dry condition I may be admixed or employed in any of the ways set forth above for treatment of the desired prod.- ucts to protect them against the development'of rancidity. i

While the application of the invention to foods forth above, the invention may similarly be applied to non-edible substances including rubber,

' resins, soaps, greases, etc., particularly when the products are in the iorm of discrete massesgand wherev the incorporation of dry materialsffor protection of such products: against development I of rancidity, or oxidative, or'aging'c'hanges are I,

particularly desirable. Similarly the invention 10 some cases,-the unfiltered material ismore ef' Having thus set forth my invention, I claim:

1. A substantially solid food material subject to oxidative change, in the form of discrete masses carrying a surface coating of a vegetative antioxidative substance. a

2. A substantially solid food substance in the form of discrete masses carrying a dust of vegetative antioxidative material on the surfaces thereof.

3. The method of protecting a substantially solid food substance subject to oxidative change which comprises applying a surface coating of a vegetative antioxidative substance to said solid substance.

4. The method of protecting a substantially solid food substance which comprises dusting said food substance with a vegetative antioxidativ material.

5. A substantially solid food material subject to oxidative change, in the form of discrete masses carrying a surface coating of oats as a p vegetative antioxidative substance.

6. A substantially solid food material subject to oxidative change, in the form of discrete masses carrying a surface coating of barley as' a vegetative antioxidative substance. 10

SIDNEY MUSHER. 

